US3699138A - Preparation of distannanes - Google Patents

Preparation of distannanes Download PDF

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Publication number
US3699138A
US3699138A US154702A US3699138DA US3699138A US 3699138 A US3699138 A US 3699138A US 154702 A US154702 A US 154702A US 3699138D A US3699138D A US 3699138DA US 3699138 A US3699138 A US 3699138A
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Prior art keywords
reaction
sodium
distannanes
temperature
halide
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Expired - Lifetime
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US154702A
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English (en)
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Eugene J Debreczeni
Bernard G Kushlefsky
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M&T Chemicals Inc
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M&T Chemicals Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/22—Tin compounds
    • C07F7/2288—Compounds with one or more Sn-metal linkages

Definitions

  • ABSTRACT Distannanes of the formula R SnSnR wherein R represents a monovalent hydrocarbon radical are prepared in high yield and purity by reacting the corresponding triorganotin halide with molten metallic sodium at elevated temperature in the absence of any solvent or diluent other than the reactants.
  • Distannanes have been prepared by reacting a trialkyltin chlordie with sodium in liquid ammonia. Such a process is commercially undesirable since it requires the use of high-pressure equipment.
  • Relatively low yields (e.g., 56 percent) of distannanes are reportedly obtained by reacting tributyltin chloride with a 20 percent excess of sodium n a hydrocarbon solvent, e.g. naphtha.
  • a hydrocarbon solvent e.g. naphtha.
  • US. Pat. No. 3,31 1,649 teaches that the yield of distannanes can be substantially increased by replacing the hydrocarbon solvent with a tetraalkyltin compound.
  • the foregoing methods leave much to be desired with regard to yield, purity, and/or volume efficiency, i.e.
  • the present invention provides an improved method for preparing distannanes of the formula R SnSnR wherein R represents a monovalent alkyl hydrocarbon radical containing between two and 12 carbon atoms inclusive, said method comprising reacting a trialkyltin halide R SnX with sodium metal, wherein the improvements comprise carrying out the reaction using molten sodium metal in the absence of any solvent or diluent other than the trialkyltin halide, permitting the reaction mixture to reach a temperature between 100 and 220C., then maintaining the reaction mixture at about 200C. until the reaction is substantially complete, and then isolating the resultant distannane.
  • the reaction between sodium metal and trialkyltin halide is often highly exothermic, and it is, therefore, preferable to have about half the sodium metal present in the initial reaction mixture. Should atmospheric moisture or other impurity which is reactive with sodium be present in the initial mixture, it is preferred to employ a slight excess of sodium metal.
  • the mixture of sodium and trialkyltin halide is heated at least to he melting point sodium, i.e., 97.5C. 'Temperatures between 170 andl80C. are preferred since at these temperatures the reaction becomes self-sustaining and the temperature often rises spontaneously to between 200 and 220C.
  • the remaining portion of sodium may be added. It is desirable to cool the reaction mixture to near ambient temperature before the second sodium addition to minimize the likelihood of splashing, spillage, or an uncontrollable reaction, all of which could result in injury to personnel operating the equipment. After completion of the second sodium addition, the
  • reaction temperature is again increased to the point where the reaction becomes self-sustaining.
  • external heating is applied to maintain the reaction mixture temperature between 180-200C. for about 2 hours or longer to ensure a substantially complete reaction.
  • the final reaction mixture contains an insoluble sodium halide salt formed as a by-product of the reaction.
  • the salt is separated from the liquid phase by any convenient means, i.e., by filtration. Any unreacted sodium will be coprecipitated with the salt.
  • the solid phase should, therefore, be combined with methanol or other alcohol to eliminate the danger of fire resulting from contact between the sodium and atmospheric moisture.
  • the liquid portion of the reaction mixture is comprised substantially entirely of the desired hexalkylditin a hexalkyl distannane, which can be used without any additional purification. If a product of greater purity is desired, the liquid phase may bedistilled. In some instances, the hexalylditin compounds, which are waterwhite when pure, may be discolored, as a result of impurities in the starting material, i.e., the trialkyltin compound.
  • the yieldof desired product can often be increased by washing the sodium halide by-product with a suitable hydrocarbon solvent, e.g., cyclohexane.
  • a suitable hydrocarbon solvent e.g., cyclohexane.
  • the sodium halide is dissolved in water and the solution extracted with the hydrocarbon solvent.
  • the hydrocarbon solvent should be relatively low boiling and, therefore, readily separable from the desired product by distillation or stripping, i.e., a relatively rapid removal of the solvent under reduced pressure.
  • Trialkyltin halides suitable for use in the process of this invention contain up to 36 carbon atoms and include compounds such as trimethyltin chloride, tri-npropyltin chloride, tri-isopropyltin chloride, tri-n-buty1- tin chloride, tri-sec-butyltin chloride, tri-n-amyltin chloride, tri-n-hexyltin chloride, tri-n-octyltin chloride, tri-n-dodecyltin chloride, etc. Any of the foregoing compounds in which the chlorine atoms are replaced by bromine are also useful providing that they are liquids at the reaction temperature, i.e., above about C.
  • trialkyltin halide may contain small amounts of impurities, e.g., monoalkyltin trihalides and dialkyltin dihalides, it is desirable to use a slight excess over the theoretical amount required by the stoichiometry of the reaction.
  • tripropyltin chloride 283.4 g. (1.0 mole) sodium metal (10) 12.6 g. (0.5 moles 5% excess) (cut into small chunks)
  • the contents of the flask were gradually heated to 103C. at which point an exothermic reaction occurred and the temperature rose spontaneously to C.
  • the exothermic portion of the reaction was temperature increased to 1 1 1C.
  • the reaction mixture was heated to 200C. for about 2 hours and then allowed to cool.
  • the excess sodium was reacted by the addition of a small portion (about 25 cc.) of methanol, followed by 100 cc. eachof cyclohexane and water, the latter being added to dissolve the sodium chloride which had precipitated during the reaction.
  • the organic phase was separated and the solvents (cyclohexane and methanol) removed by distillation.
  • the residue weighted 208 g. (84 percent yield) and exhibited the following analysis:
  • the liquid from the washing was concentrated under reduced pressure to yield 487 g. of a clear, yellow liquid.
  • the combined liquid phases weighted 1,41 1.4 g. (81.2 percent yield).
  • the two liquids were analyzed with the following results.
  • bromine number is equal to'the percent of bromine (based on sample weight). which will react with the sample.
  • One mole of bromine is believed to react with one mole of distannane toyielcl 2 moles of a triorganotin bromide.
  • R is selected from the group consisting of propyl, butyl, and hexyl radicals and X is chlorine or bromine.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US154702A 1971-06-18 1971-06-18 Preparation of distannanes Expired - Lifetime US3699138A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US15470271A 1971-06-18 1971-06-18

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US3699138A true US3699138A (en) 1972-10-17

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Country Status (7)

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US (1) US3699138A (fr)
JP (1) JPS577156B1 (fr)
CA (1) CA956322A (fr)
DE (1) DE2226774C3 (fr)
FR (1) FR2142013B1 (fr)
GB (1) GB1352300A (fr)
NL (1) NL174356C (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU571081B2 (en) * 1984-06-26 1988-03-31 Mobil Oil Corp. Preparation of zeolite zsm-12
US5298641A (en) * 1992-09-17 1994-03-29 Witco Gmbh Method of preparing distannanes
EP0682035A2 (fr) * 1994-05-13 1995-11-15 Bridgestone Corporation Préparation de compositions de triorganoétain et lithium et leur utilisation comme initiateurs
US5488091A (en) * 1994-06-24 1996-01-30 The Regents Of The University Of California High molecular weight polystannanes by metal-catalyzed dehydropolymerization
US5847064A (en) * 1997-02-27 1998-12-08 University Of Florida Polycarbometallanes via acyclic diene metathesis polymerization

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61116057U (fr) * 1984-12-28 1986-07-22
JPS61116056U (fr) * 1984-12-28 1986-07-22

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2965661A (en) * 1956-05-09 1960-12-20 Metal & Thermit Corp Vinylic tin compounds
US3027393A (en) * 1956-07-14 1962-03-27 Kali Chemie Ag Preparation of organotin compounds
US3105000A (en) * 1961-05-25 1963-09-24 Dow Chemical Co Organo-tin and organo-sulphur parasiticides
US3132070A (en) * 1962-03-16 1964-05-05 Stauffer Chemical Co Method of controlling fungus by means of organotin compounds
US3311649A (en) * 1964-11-30 1967-03-28 Carlisle Chemical Works Preparation of distannanes

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2965661A (en) * 1956-05-09 1960-12-20 Metal & Thermit Corp Vinylic tin compounds
US3027393A (en) * 1956-07-14 1962-03-27 Kali Chemie Ag Preparation of organotin compounds
US3105000A (en) * 1961-05-25 1963-09-24 Dow Chemical Co Organo-tin and organo-sulphur parasiticides
US3132070A (en) * 1962-03-16 1964-05-05 Stauffer Chemical Co Method of controlling fungus by means of organotin compounds
US3311649A (en) * 1964-11-30 1967-03-28 Carlisle Chemical Works Preparation of distannanes

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU571081B2 (en) * 1984-06-26 1988-03-31 Mobil Oil Corp. Preparation of zeolite zsm-12
US5298641A (en) * 1992-09-17 1994-03-29 Witco Gmbh Method of preparing distannanes
EP0682035A2 (fr) * 1994-05-13 1995-11-15 Bridgestone Corporation Préparation de compositions de triorganoétain et lithium et leur utilisation comme initiateurs
EP0682035A3 (fr) * 1994-05-13 1998-05-20 Bridgestone Corporation Préparation de compositions de triorganoétain et lithium et leur utilisation comme initiateurs
US5488091A (en) * 1994-06-24 1996-01-30 The Regents Of The University Of California High molecular weight polystannanes by metal-catalyzed dehydropolymerization
US5847064A (en) * 1997-02-27 1998-12-08 University Of Florida Polycarbometallanes via acyclic diene metathesis polymerization

Also Published As

Publication number Publication date
NL174356B (nl) 1984-01-02
NL7208278A (fr) 1972-12-20
DE2226774A1 (de) 1972-12-21
NL174356C (nl) 1984-06-01
FR2142013A1 (fr) 1973-01-26
JPS577156B1 (fr) 1982-02-09
CA956322A (en) 1974-10-15
DE2226774B2 (de) 1980-11-27
DE2226774C3 (de) 1981-12-10
FR2142013B1 (fr) 1977-06-17
GB1352300A (en) 1974-05-08

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